CN207690927U - A kind of iron-based redox flow battery system - Google Patents
A kind of iron-based redox flow battery system Download PDFInfo
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- CN207690927U CN207690927U CN201721814054.7U CN201721814054U CN207690927U CN 207690927 U CN207690927 U CN 207690927U CN 201721814054 U CN201721814054 U CN 201721814054U CN 207690927 U CN207690927 U CN 207690927U
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Abstract
The utility model discloses a kind of iron-based redox flow battery system, including electroplated electrode, oxidation-reduction electrode, electroplating electrolytes storage tank, redox electrolyte storage tank, first reactor, second reactor, control system, monitoring device；The electroplating electrolytes storage tank is to store plating bath, and the redox electrolyte storage tank is storing redox electrolytes liquid；The oxidation-reduction electrode will be fluidly coupled to redox electrolyte storage tank, and the electroplated electrode will be fluidly coupled to electroplating electrolytes storage tank；The electroplating electrolytes storage tank connects first reactor by the first transfer pipeline, and redox electrolyte storage tank connects second reactor by the second transfer pipeline；The control system connects monitoring device.The utility model proposes iron-based redox flow battery system, can be promoted battery system performance, improve battery system efficiency.
Description
Technical field
The utility model belongs to battery technology field, is related to a kind of battery system more particularly to a kind of iron-based redox
Flow battery system.
Background technology
Redox flow batteries are a kind of electrochemical storage devices, it is stored energy in a kind of chemical substance, are led to
It crosses spontaneous anti-redox reaction and converts the chemical energy of storage to electric energy.Reaction in flow battery is reversible, anti-mistake
For, the chemical energy of distribution can be restored by inducing the electric current of reversed redox reaction.Single redox flow galvanic electricity
Pond generally comprises cathode, film barrier layer, anode and the electrolyte containing electroactive material.Multiple batteries can with serial or parallel connection,
To generate higher voltage or electric current in galvanic battery.Electrolyte is commonly stored in external container, and pass through battery two
Side is pumped.When applying charge current, electrolyte loses electronics in anode, and electronics is obtained on cathode.Envelope barrier is anti-
Only catholyte and the mixing of negative electrolyte, while allowing ionic conduction.When applying discharge current, reversed oxygen occurs on electrode
Change reduction reaction.Potential difference in battery is maintained by the redox reaction in electrolyte, and in response duration energy
Pass through conductor induced current.The energy of redox cell storage limiting for the electroactive material quantity of electric discharge in by electrolyte
System, this depends on the solubility of the total volume and electroactive material of electrolyte.
Mixing flow battery is to deposit solid layer on the electrode by one or more electroactive materials to distinguish.Example
Such as, mixing flow battery may include a kind of chemical substance, it is used as solid, discharge in entire charging process on substrate
Substance can be dissolved by the electrolyte in entire discharge process.In mixing flow battery system, redox cell storage
Energy may be limited by amount of metal is plated in charging process, it is thus possible to depend on the efficiency of electroplating system and available
Volume and surface area.
In mixing flow battery system, cathode is properly termed as electroplated electrode, and anode is properly termed as oxidation-reduction electrode.Electricity
The electrolyte of pond plating side is properly termed as electroplating electrolytes, and the electrolyte of cell oxidation reduction side is properly termed as redox electrolytes
Matter.
One example of hybrid redox flow batteries is electrolyte of the iron as reaction, the Fe on cathode2+It is filling
Two electronics are received in electric process, are deposited in the form of metallic iron, and iron loses two electronics and again molten in discharge process
Solution is Fe2+.On anode, two Fe2+Two are lost in charging process electronically forms two Fe3+, in discharge process, two
A Fe3+It obtains two and electronically forms two Fe2+：
Electrolyte for this reaction is ready-made, can be produced in low cost (such as frerrous chloride).It equally has
There is very high recovery value, because identical electrolyte can be used for electroplating electrolytes and redox electrolyte, is handed over to eliminate
Pitch the possibility of pollution.It is different that other compounds for using in galvanic battery are restored from mixed oxidization, iron not shape in electroplating process
At dendron, to provide stable electrode shape.In addition, iron oxidation reduction reflux battery need not use toxic raw materials, opposite
It works under neutral pH, it is different from similar oxidation reduction reflux battery electrolyte.Therefore, it is all advanced electricity produced at present
To the product of environmental hazard minimum in cell system.
However, the shortcomings that above system, limits its practicability in commercial applications.One of these disadvantages are due to this
The pH value range that a little cathode and redox electrolyte tend towards stability is different, causes the cycle performance of these batteries and efficiency low
Under.In order to reduce the corrosion reaction of iron and improve plating iron efficiency, plating iron reaction needs 3~4 pH value.However, ferrous ion and
PH value needed for ferrous ions oxidation reduction reaction is less than 1, to promote dynamics of oxidation-reduction, and reduces hydroxide to the greatest extent
Generation.
The intersection of electrolyte can be caused by detaching the concentration gradient of the envelope barrier of electrolyte.From redox side (acid stronger)
To the Fe of plating side (acid relatively low)3+Pollution can lead to Fe (OH)3Sediment formation.This sediment can destroy ion friendship
Change the organo-functional group of film or the micropore of blocking microporous film.In both cases, film Ohmic resistance is over time
And rise, battery performance declines.
In view of this, nowadays there is an urgent need to design a kind of new battery system, to overcome existing for existing battery system
Drawbacks described above.
Utility model content
Technical problem to be solved in the utility model is：A kind of iron-based redox flow battery system is provided, can be dropped
The formation that low Fe (OH) 3 is precipitated, promotes the performance and stability of battery system.
In order to solve the above technical problems, the utility model adopts the following technical solution：
A kind of iron-based redox flow battery system, the battery system include：Control system, electroplating electrolytes storage
Tank, redox electrolyte storage tank, first sensor, second sensor, the first external reservoir, the second external reservoir, cathode add
Add agent pump, anode additive pump, cathode, anode, cathode plating iron layer, diaphragm, cathode reactor, anode reactor, the first probe,
Second probe, first pump housing, second pump housing；
The control system is separately connected first sensor, second sensor, the first probe, the second probe, cathode addition
Agent pump, anode additive pump, first pump housing, second pump housing, the control system receive first sensor, second sensor, the
The data of one probe, the second probe induced, control cathode additive pump, anode additive pump, first pump housing, second pump housing move
Make；Electrolyte can be pumped out by first pump housing, second pump housing from reactor；
The first sensor, second sensor are used to determine the chemical property of electrolyte, including pH value, and as light
Sensor is learned to use；First probe, the second probe are used to measure the chemical property of electrolyte；
The effect of the electroplating electrolytes storage tank, redox electrolyte storage tank is storage electrolyte；The effect of electrolyte
It is to be chemically reacted in charging process, stores electricity, again discharge the charge in electrolyte in discharge process；
The effect of first external reservoir and the second external reservoir is that storage plating bath additive, oxidation are gone back respectively
Original electrolyte additive changes to the electrolyte ph in electroplating electrolytes storage tank, redox electrolyte storage tank
When, it is pumped into additive, to adjust pH value；
First external reservoir, the second external reservoir store cathode additive, anode additive respectively；Outside described first
Portion's storage tank pumps connection cathode reactor by cathode additive, and the second external reservoir pumps jointed anode by anode additive and reacts
Device；First external reservoir, the second external reservoir will can be fluidly coupled to cathode reactor, the anode reaction of battery system respectively
Device；Electrolysis additive can be pumped into corresponding electroplating electrolytes storage tank, oxidation from the first external reservoir, the second external reservoir respectively
Also original electrolyte storage tank；
The electroplating electrolytes storage tank is pumped by two piping connection cathode reactors, wherein a pipeline setting first
Body, wherein pipeline first sensor is set；
The redox electrolyte storage tank is by two piping connection anode reactors, one article of pipeline setting wherein the
Two pump housings, wherein pipeline second sensor is set；
The cathode, cathode plating iron layer, cathode reactor, diaphragm, anode reactor, anode are set gradually；
The diaphragm is being isolated cloudy reactor, positive reactor and its respective electrolyte；The diaphragm is envelope barrier, is
Amberplex or microporous barrier are placed between redox electrolytes liquid and plating bath, to prevent electrolyte from intersecting and carry
For ionic conductivity；
The electroplating electrolytes storage tank to store plating bath, to store oxidation go back by redox electrolyte storage tank
Former electrolyte；The plating bath and redox electrolytes liquid are all made of identical metal salt, and only its concentration is different；
The anode is oxidation-reduction electrode, will be fluidly coupled to redox electrolyte storage tank；The cathode is plating
Electrode will be fluidly coupled to electroplating electrolytes storage tank.
A kind of iron-based redox flow battery system, which is characterized in that the battery system includes：Electroplated electrode, oxygen
Change reducing electrode, electroplating electrolytes storage tank, redox electrolyte storage tank, first reactor, second reactor, control system,
Monitoring device, the first external reservoir, the second external reservoir；
The electroplating electrolytes storage tank is to store plating bath, and the redox electrolyte storage tank is storing oxygen
Change reduction electrolyte；
The oxidation-reduction electrode will be fluidly coupled to redox electrolyte storage tank, and the electroplated electrode is by fluid coupling
To electroplating electrolytes storage tank；
The electroplating electrolytes storage tank connects first reactor by the first transfer pipeline, and redox electrolyte storage tank is logical
Cross the second transfer pipeline connection second reactor；The first reactor connects electroplated electrode, and the second reactor connects oxygen
Change reducing electrode；
The monitoring device to detect in the electroplating electrolytes storage tank or/and in redox electrolyte storage tank or/
With the first transfer pipeline or/and the chemical property of the second transfer pipeline Inner electrolysis matter；
The control system connects monitoring device, and the first outside of data control monitored according to the monitoring device is stored up
Tank, the second external reservoir additive be pumped into toward electrolyte storage tank.
As a kind of preferred embodiment of the utility model, the electroplating electrolytes storage tank, redox electrolyte storage tank
Effect is storage electrolyte；The effect of electrolyte is chemically reacted in charging process, electricity is stored, in discharge process
The charge in electrolyte is discharged again；
The effect of first external reservoir and the second external reservoir is that storage plating bath additive, oxidation are gone back respectively
Original electrolyte additive changes to the electrolyte ph in electroplating electrolytes storage tank, redox electrolyte storage tank
When, it is pumped into additive, to adjust pH value.
As a kind of preferred embodiment of the utility model, the battery system further includes cathode additive pump, anode addition
Agent pump, first pump housing, second pump housing；The control system is separately connected the first additive pump, Second addition pump, the first pump
Body, second pump housing；The first reactor is cathode reactor, and second reactor is anode reactor；
First external reservoir, the second external reservoir store cathode additive, anode additive respectively；Outside described first
Portion's storage tank pumps connection cathode reactor by cathode additive, and the second external reservoir pumps jointed anode by anode additive and reacts
Device；First external reservoir, the second external reservoir will can be fluidly coupled to cathode reactor, the anode reaction of battery system respectively
Device；
The electroplating electrolytes storage tank connects electroplated electrode by third transfer pipeline, and the third transfer pipeline is equipped with the
One pump housing；
The redox electrolyte storage tank connects oxidation-reduction electrode, the 4th delivery pipe by the 4th transfer pipeline
Road is equipped with second pump housing.
As a kind of preferred embodiment of the utility model, electroplating electrolytes or redox electrolyte include FeCl2、FeCl3
Or their arbitrary combination；
The monitoring device includes Fe potential probes, by clean an iron wire and reference electrode, such as Ag/AgCl electrodes
Or H2Electrode is connected；
Plating bath additive, redox electrolyte additive include boric acid, ascorbic acid, acetic acid, malic acid, breast
Acid, citric acid, tartaric acid, arabo-ascorbic acid, malonic acid, glycolic or their arbitrary combination.
As a kind of preferred embodiment of the utility model, the monitoring device includes first sensor, second sensor, and
One sensor is set to the first transfer pipeline, and second sensor is set to the second transfer pipeline；The first sensor, second pass
Sensor is used to determine the chemical property of electrolyte, including pH value；Alternatively,
The monitoring device include the first probe, the second probe part be respectively arranged at electroplating electrolytes storage tank, oxidation
Also in original electrolyte storage tank, the chemical property for measuring electrolyte.
As a kind of preferred embodiment of the utility model, cathode plating iron is equipped between the electroplated electrode and first reactor
Layer.
As a kind of preferred embodiment of the utility model, diaphragm is equipped between the first reactor and second reactor.
As a kind of preferred embodiment of the utility model, the electroplated electrode is cathode, and the oxidation-reduction electrode is sun
Pole；It is equipped with cathode between the electroplated electrode and first reactor and plates iron layer；Between the cathode reactor and anode reactor
Equipped with diaphragm；The cathode, cathode plating iron layer, cathode reactor, diaphragm, anode reactor, anode are set gradually；
The diaphragm is being isolated cloudy reactor, positive reactor and its respective electrolyte；The diaphragm is envelope barrier, is
Amberplex or microporous barrier are placed between redox electrolytes liquid and plating bath, to prevent electrolyte from intersecting and carry
For ionic conductivity；
The electroplating electrolytes storage tank to store plating bath, to store oxidation go back by redox electrolyte storage tank
Former electrolyte；The plating bath and redox electrolytes liquid are all made of identical metal salt, and only its concentration is different；
The anode is oxidation-reduction electrode, will be fluidly coupled to redox electrolyte storage tank；The cathode is plating
Electrode will be fluidly coupled to electroplating electrolytes storage tank；
As a kind of preferred embodiment of the utility model, these may contain different additives and by different program controls
System；Full iron liquid galvanic battery IFB has anode additive or cathode additive；
In cell operation, the concentration gradient of diaphragm both sides drives a large amount of Fe3+From redox electrolytes liquid to electricity
Plating electrolyte solution；From plating bath to redox electrolytes liquid, the change dramatically of pH value leads to Fe (OH) (from 1 to 3-6)3Species
Formation and precipitation；These sediments are degraded by the aperture of the organo-functional group or blocking microporous film that poison amberplex
Exchange membrane rises so as to cause the Ohmic resistance of battery.Sediment, but frequent maintenance limitation can be removed with acid cleaning battery
In the business application of battery, it also relies on the regular preparation of electrolyte；By to the corresponding of electrolyte pH, to electrolyte
It is middle that specific organic acid is added to inhibit above-mentioned reaction；
Electrolyte is pumped by respective electrode in IFB systems；The electrolyte ph of battery is measured using iron probe
Electrolyte potential is measured with reference electrode, includes the Ag/AgCl or H of electroplated electrode2Electrode；In addition, by using optical sensing
Device measures the reflectance spectrum of electrolyte to monitor pH value；Other specified pH sensing devices are also used for pH measurement；
Sensor and/or probe convey the pH value of electrolyte to control system；If it find that the pH value of plating solution is higher than setting
First threshold, then control system actuate the burst size of pretreated acid, which can be added in electroplating electrolytes；If it find that oxygen
Change and go back the pH of original electrolyte higher than setting second threshold, then control system actuates the burst size of previously prepared acid to redox
Electrolyte；The acid additives for being added to cathode and anode are identical or different, including boric acid, ascorbic acid, glycolic or they
Arbitrary combination；The process may repeat, until pH value is less than threshold value；If pH value less than threshold value IFB will continue to charging or
Electric discharge；
Best plating iron layer is realized using the combination of organic additive, to improve its performance, efficiency and stability；
FeCl2In NaCl electrolyte solutions, boric acid is added to inhibit H2Side reaction and raising coulombic efficiency；In addition, addition ascorbic acid
To improve the stability of iron ion, and glycolic is added to reduce the generation of carbon；
In the negative side of IFB systems, the Fe in charging process2+Receive two and electronically forms Fe0；In the competing of battery cathode side
Strive reaction, H+Receive one and electronically forms H2, the electrolyte ph of IFB negative sides can be caused to be stepped up to 6 from 2, by above-mentioned
Probe and Sensor monitoring pH value variation；
PH variations may cause battery to cause up to 100 millivolts of apparent property to damage due to high balance potential drifting
It loses.In order to mitigate performance loss, Fe current potentials probe or optical sensor are used to monitor the pH of the charged state and electrolyte of battery
Value is horizontal；
The action pane pH value of battery plating bath is between 3 and 4；When Fe potential probes or optical sensor are shown
The acid precalculated on a small quantity is added in electroplating electrolytes solution by pH value at 4 or more, by electroplated electrode back to most preferably
PH ranges.
The beneficial effects of the utility model are：The utility model proposes iron-based redox flow battery system, can
It promotes the performance of battery system, improve the efficiency of battery system.
The utility model solves what cathode and redox electrolyte in full iron redox flow batteries tended towards stability
PH value range is different, and the cycle performance of battery and inefficiency and the intersection of electrolyte is caused to lead to Fe (OH)3Sediment
Formation, the technical issues of final film Ohmic resistance rises over time, and battery performance declines.
The utility model can reduce Fe (OH) by the chelating agent of the organic compound form of addition3The shape of precipitation
At.These organic compounds can form compound, wherein Fe3+It is transitioned into plating side from redox side.These compounds exist
It is more soluble in acidic environment, to stabilize iron ion.
In addition, the color and current potential of these complicated compounds are related to the pH value of solution.Therefore, the utility model passes through
The pH of optical sensor and/or electrochemical probe monitoring electrolyte, to realize the metering to the chemical addition agent of addition, with reality
Now with maintain electrolyte needed for pH, to prevent precipitate and preserve coulombic efficiency.
Description of the drawings
Fig. 1 is full iron redox flow battery system structural schematic diagram disclosed by the utility model.
Fig. 2 is the coulomb electroplating efficiency of the pH value of two different acid additives.
Fig. 3 is the relational graph of the color and pH value of electrolyte.
Attached drawing mark is as follows：
01-- electroplating electrolytes storage tanks；02-- redox electrolyte storage tanks；03-sensor；04-sensor；
05-the first external reservoir；06-the second external reservoir；07-cathode additive pumps；08-anode additive pumps；
09-cathode；10-anodes；11-cathodes plate iron layer；12-diaphragms；
13-cathode reactors；14-anode reactors；15-probes；16-probes；
17-the first pump housing；18-the second pump housing.
Specific implementation mode
The preferred embodiment that according to the present invention will be described in detail below with reference to the accompanying drawings.
Embodiment one
Referring to Fig. 1, the utility model discloses a kind of iron-based redox flow battery system, the battery system packet
It includes：Control system, electroplating electrolytes storage tank 01, redox electrolyte storage tank 02, first sensor 03, second sensor 04,
First external reservoir 05, the second external reservoir 06, cathode additive pump 07, anode additive pump 08, cathode 9, anode 10, cathode
Plate iron layer 11, diaphragm 12, cathode reactor 13, anode reactor 14, the first probe 15, the second probe 16, first pump housing 17, the
Two pump housings 18；
The control system be separately connected first sensor 03, second sensor 04, the first probe 15, the second probe 16,
Cathode additive pump 07, anode additive pump 08, first pump housing 17, second pump housing 18, and the control system receives the first sensing
The data that device 03, second sensor 04, the first probe 15, the second probe 16 incude, control cathode additive pump 07, anode addition
Agent pumps the action of 08, first pump housing 17, second pump housing 18；Electrolyte can be from reactor by first pump housing 17, second pump housing 18
It is pumped out in (cathode reactor 13, anode reactor 14).
The first sensor 03, second sensor 04 are used to determine the chemical property of electrolyte, including pH value, and make
It is used for optical sensor；First probe, the second probe are used to measure the chemical property of electrolyte.
The effect of the electroplating electrolytes storage tank, redox electrolyte storage tank is storage electrolyte；The effect of electrolyte
It is to be chemically reacted in charging process, stores electricity, again discharge the charge in electrolyte in discharge process.
The effect of first external reservoir and the second external reservoir is that storage plating bath additive, oxidation are gone back respectively
Original electrolyte additive changes to the electrolyte ph in electroplating electrolytes storage tank, redox electrolyte storage tank
When, it is pumped into additive, to adjust pH value.
First external reservoir 05, the second external reservoir 06 store cathode additive, anode additive respectively；Described
One external reservoir 05 pumps connection cathode reactor 13 by cathode additive, and the second external reservoir 06 is pumped by anode additive to be connected
Connect anode reactor 14；First external reservoir 05, the second external reservoir 06 will can be fluidly coupled to the cathode of battery system respectively
Reactor 13, anode reactor 14；Electrolysis additive can be pumped into pair from the first external reservoir 05, the second external reservoir 06 respectively
Electroplating electrolytes storage tank 01, the redox electrolyte storage tank 02 answered.
The electroplating electrolytes storage tank 01 is by two piping connection cathode reactors 13, one article of pipeline setting wherein the
One pump housing 17, wherein pipeline first sensor 03 is set；The redox electrolyte storage tank 02 passes through two pipelines
Jointed anode reactor 14, wherein pipeline second pump housing 18 is set, second sensor 04 is arranged in a pipeline wherein.
The cathode 09, cathode plating iron layer 11, cathode reactor 13, diaphragm 12, anode reactor 14, anode 10 are set successively
It sets.
The diaphragm 12 is being isolated cloudy reactor 13, positive reactor 14 and its respective electrolyte；The diaphragm 12 is
Envelope barrier is amberplex or microporous barrier, is placed between redox electrolytes liquid and plating bath, to prevent electrolyte
Intersect and ionic conductivity is provided.
The electroplating electrolytes storage tank 01 is to store plating bath, and redox electrolyte storage tank 02 is storing oxygen
Change reduction electrolyte；The plating bath and redox electrolytes liquid can be all made of identical metal salt, only its concentration
It is different.
The anode 10 is oxidation-reduction electrode, will be fluidly coupled to redox electrolyte storage tank 02；The cathode 09
For electroplated electrode, electroplating electrolytes storage tank 01 will be fluidly coupled to.
The battery system can be applied to IFB (full iron liquid galvanic battery, All Iron Flow Battery) system；Also
It can be used for iron zinc flow battery, as long as the flow battery system containing Fe ions can be applied.In I FB, these may
It is controlled containing different additives and by different programs；IFB (full iron liquid galvanic battery, All Iron Flow Battery) has
Anode additive or cathode additive.
In cell operation, the concentration gradient of diaphragm both sides drives a large amount of Fe3+From redox electrolytes liquid to electricity
Plating electrolyte solution；From plating bath to redox electrolytes liquid, the change dramatically of pH value leads to Fe (OH)3The formation of species and heavy
It forms sediment；These sediments by poisoning the organo-functional group of amberplex or the aperture of blocking microporous film come exchange membrane of degrading, from
And the Ohmic resistance of battery is caused to rise；Sediment is removed with acid cleaning battery, but frequent maintenance limits the business of battery
In, it also relies on the regular preparation of electrolyte；By to the corresponding of electrolyte pH, being added into electrolyte specific
Organic acid inhibits above-mentioned reaction.
Electrolyte is pumped by respective electrode in IFB systems；The electrolyte ph of battery is measured using iron probe
Electrolyte potential is measured with reference electrode, includes the Ag/AgCl or H of electroplated electrode2Electrode；In addition, by using optical sensing
Device measures the reflectance spectrum of electrolyte to monitor pH value；Other specified pH sensing devices are also used for pH measurement.
Sensor and/or probe convey the pH value of electrolyte to control system；If it find that the pH value of plating solution is higher than setting
First threshold, then control system actuate the burst size of pretreated acid, which can be added in electroplating electrolytes；If it find that oxygen
Change and go back the pH of original electrolyte higher than setting second threshold, then control system actuates the burst size of previously prepared acid to redox
Electrolyte；The acid additives for being added to cathode and anode are identical or different, including boric acid, ascorbic acid, glycolic or they
Arbitrary combination；The process may repeat, until pH value is less than threshold value；If pH value less than threshold value IFB will continue to charging or
Electric discharge.
Best plating iron layer is realized using the combination of organic additive, to improve its performance, efficiency and stability；
FeCl2In NaCl electrolyte solutions, boric acid is added to inhibit H2Side reaction and raising coulombic efficiency；In addition, addition ascorbic acid
To improve the stability of iron ion, and glycolic is added to reduce the generation of carbon.
In the negative side of IFB systems, the Fe in charging process2+Receive two and electronically forms Fe0；In the competing of battery cathode side
Strive reaction, H+Receive one and electronically forms H2, the electrolyte ph of IFB negative sides can be caused to be stepped up to 6 from 2, by above-mentioned
Probe and Sensor monitoring pH value variation.
PH variations may cause battery to cause up to 100 millivolts of apparent property to damage due to high balance potential drifting
It loses.In order to mitigate performance loss, Fe current potentials probe or optical sensor are used to monitor the pH of the charged state and electrolyte of battery
Value is horizontal.
The action pane pH value of battery plating bath is between 3 and 4；When Fe potential probes or optical sensor are shown
The acid precalculated on a small quantity is added in electroplating electrolytes solution by pH value at 4 or more, by electroplated electrode back to most preferably
PH ranges.
Embodiment two
As shown in Figure 1, for the embodiment of full iron redox flow batteries (IFB) system.Plating bath can store up
There are in electroplating electrolytes storage tank, redox electrolytes liquid can be stored in redox electrolyte storage tank.Plating bath and
Electrolyte may be that a suitable salt is dissolved in water, such as FeCl2And FeCl3.Either electroplate liquid and electrolyte is all made of phase
Same metal salt, only its concentration is different.Two external reservoirs can be fluidly coupled to the anode reactor 14 and cathode of battery
Reactor 13.It is diaphragm 12 that yin, yang reactor and its respective electrolyte, which is isolated,.The diaphragm can be envelope barrier, such as ion
Exchange membrane or microporous barrier are placed between redox electrolytes liquid and plating bath, with prevent electrolyte from intersecting and provide from
Subconductivity.Sensor 03 and 04 can be used for determining the chemical property of electrolyte, including pH value, and can be used as optical sensing
Device uses.Probe 15 and 16 can chemical property that is other or being alternately used in measurement electrolyte.Other embodiments can have
Electroplating electrolytes probe, electroplating electrolytes sensor, redox electrolyte probe, redox electrolyte sensor or one
A little combinations.Acid additive can be placed in external reservoir 05 and 06.These may contain different additives and by different journeys
Sequence controls.In other embodiments, IFB may also have anode additive or cathode additive.It can by anode additive pump 08
Anode additive is pumped into anode reactor 13, cathode additive can pump 07 by cathode additive and be pumped into cathode reactor
In 14.Electrolysis additive is pumped into storage tank 01 and 02.The control system that pump 13 and 14 can be communicatively connected to pump by one
It is driven.Control system may be in response to probe 15, probe 16, sensor 03, sensor 04.Electrolyte can
To be pumped out from reactor by pump 17.
In cell operation, the concentration gradient of diaphragm both sides drives a large amount of Fe3+From redox electrolytes liquid to electricity
Plating electrolyte solution.From plating bath to redox electrolytes liquid, the change dramatically of pH value leads to Fe (OH) (from 1 to 3-6)3Species
Formation and precipitation.These sediments are degraded by the aperture of the organo-functional group or blocking microporous film that poison amberplex
Exchange membrane rises so as to cause the Ohmic resistance of battery.Sediment, but frequent maintenance limitation can be removed with acid cleaning battery
In the business application of battery, it also relies on the regular preparation of electrolyte.However, method disclosed herein passes through to electrolysis
Matter pH value it is corresponding, specific organic acid is added into electrolyte to inhibit above-mentioned reaction.
Electrolyte can be pumped by respective electrode in IFB systems.The electrolyte ph of battery can use iron
Probe measures electrolyte potential and is measured with reference electrode, such as the Ag/AgCl or H of electroplated electrode2Electrode.Furthermore it is possible to by making
PH value is monitored with the reflectance spectrum of optics sensor measures electrolyte.Other specified pH sensing devices can also be used for pH surveys
It is fixed.
In the present invention, sensor and/or probe can convey the pH value of electrolyte to control system.If it find that
The pH value of plating solution is higher than threshold value, and such as pH ＞ 4, then control system can actuate the burst size of pretreated acid, which can be added to electricity
It plates in electrolyte.If it find that the pH of redox electrolyte is higher than threshold value, such as pH ＞ 1, then control system can actuate advance system
The burst size of standby acid is to redox electrolyte.The acid additives for being added to cathode and anode can be identical or different, can
Can include but not limited to boric acid, ascorbic acid, glycolic or their arbitrary combination.The process may repeat, until pH value is low
In threshold value.If pH value may continue to charge or discharge less than the IFB of threshold value.
The disclosed embodiments are asked to realize above-mentioned by the way that specific chemicals (acid additive) is added in the electrolyte
Inscribe the inhibition of reaction.Acid additives in electrolyte can stablize the Fe from redox electrolyte to plating bath3+It hands over
It changes, therefore, the acid additive used in the present embodiment has specific chemical property.The acid studied and their some attributes
It is listed in Table 1 below.
Table 1 is used to stablize the organic acid test of IFB electrolyte
2 organic acid-Fe of table2+/Fe3+Stability at various ph values
Fe of the utility model to different ratio：Organic acid has carried out identical H- battery testings, studies under different pH value
The stability of the intersection iron ion of electroplated layer, as shown in Figure 2.In the embodiment of this system, the knot of Fig. 2 is utilized by control system
Fruit realizes that required coulombic efficiency corresponds to the pH needed for electrolytic solution to determine.Fig. 2 describes different pH value in a graphical form
The plating iron coulombic efficiency of plating solution.As shown in table 2 and Fig. 2, simple acetic acid and glycolic cannot stablize friendship under high pH conditions
Pitch iron ion.However, individual ascorbic acid or arabo-ascorbic acid are undesirable to use as organic acid, because of the shape of C
At the reduction that can lead to coulombic efficiency.Surface sweeping is carried out to the iron plating for only adding ascorbic acid formation with scanning electron microscope to detect carbon
Formational situation.
Therefore, in the embodiments of the present invention, best plating can be realized using the combination of organic additive
Iron layer, to improve its performance, efficiency and stability.In embodiment, in FeCl2In NaCl electrolyte solutions, addition first
Sour (such as boric acid) is planted to inhibit H2Side reaction and raising coulombic efficiency.Further, it is also possible to add second sour (such as ascorbic acid) with
The stability of iron ion is improved, and the third sour (such as glycolic) is added to reduce the generation of carbon.
In the other embodiments of the system of the utility model, the pH of electrolyte also can by can be used alone or with probe knot
Close the Sensor monitoring used.In embodiment, optical sensor can be by the absorption spectrum of liquid measure ambient light with determination
Corresponding pH value.If chelating organic acid is added in the electrolytic solution to improve iron ion stability, optical sensor can also be used for
Monitor the state of charge of battery.This is because chelating iron complex shows different colors in different pH value.For example, such as
Fruit ascorbic acid makees chelating agent, and during the pH value of solution changes from 2 to 6, the color of ferrous solution becomes purple from green,
Eventually become black.
Being communicatively coupled to the control system of sensor can be judged using the relationship of pH value depicted in figure 3 and color
PH value.In pH- color relationship figures, the longitudinal axis indicates the H of each carbon atom binding+Average, horizontal axis Logh.Such as Fig. 3 institutes
Show, at low ph values, green or white is presented in solution, and with the increase of pH value, solution gradually becomes purple, and eventually becomes black
Color.The light reflected by the wavelength of measuring environment light or from known source and/or by electrolyte, it may be determined that the pH of electrolyte
Value.
In embodiment, white light can be incident on the surface of electrolyte.Spectroscope can be used with true in sensor
The wavelength of the fixed light reflected by electrolyte.If a reflection or transmission peak wavelength are found, for example, (corresponding to purple less than 450nm
Color) acid solution in additive is added can reduce the pH value of electrolyte.In addition, spectroscope can continue to monitor the suction of electrolyte
Spectrum is received, if reflection and/or launch wavelength find more than one threshold value, if 510nm (corresponds to green), acid additives
Addition can terminate.
In the negative side of IFB systems, the Fe in charging process2+Receive two and electronically forms Fe0.In the competing of battery cathode side
Strive reaction (H+Receive one and electronically forms H2) electrolyte ph of IFB negative sides can be caused to be stepped up to 6 from 2, therefore at this
The variation of probe above and Sensor monitoring pH value can be used in the embodiment of utility model system.
PH variations may cause battery to cause up to 100 millivolts of apparent property to damage due to high balance potential drifting
It loses.In order to mitigate performance loss, such as embodiment of above-mentioned sensor, this disclosed Fe current potential is popped one's head in or optical sensor,
It can be used for monitoring the pH level of the charged state and electrolyte of battery.
The action pane pH value of battery plating bath is between 3 and 4.Therefore, in embodiment, when Fe potential probes
Or optical sensor shows that the acid precalculated on a small quantity at 4 or more, can be added in electroplating electrolytes solution by pH value, with
Electroplated electrode is returned into optimum PH range.As a result, battery performance can be stablized.
Embodiment three
A kind of iron-based redox flow battery system, the battery system include：Electroplated electrode, oxidation-reduction electrode,
Electroplating electrolytes storage tank, redox electrolyte storage tank, first reactor, second reactor, the first external reservoir, outside second
Storage tank, control system, monitoring device；
The electroplating electrolytes storage tank is to store plating bath, and the redox electrolyte storage tank is storing oxygen
Change reduction electrolyte；
The oxidation-reduction electrode will be fluidly coupled to redox electrolyte storage tank, and the electroplated electrode is by fluid coupling
To electroplating electrolytes storage tank；
The electroplating electrolytes storage tank connects first reactor by the first transfer pipeline, and redox electrolyte storage tank is logical
Cross the second transfer pipeline connection second reactor；The first reactor connects electroplated electrode, and the second reactor connects oxygen
Change reducing electrode；
The monitoring device to detect in the electroplating electrolytes storage tank or/and in redox electrolyte storage tank or/
With the first transfer pipeline or/and the chemical property of the second transfer pipeline Inner electrolysis matter；
The control system connects monitoring device, and the first outside of data control monitored according to the monitoring device is stored up
Tank, the second external reservoir additive be pumped into toward electrolyte storage tank.
In conclusion the utility model proposes iron-based redox flow battery system, the property of battery system can be promoted
It can, improve the efficiency of battery system.
The utility model solves what cathode and redox electrolyte in full iron redox flow batteries tended towards stability
PH value range is different, and the cycle performance of battery and inefficiency and the intersection of electrolyte is caused to lead to Fe (OH)3Sediment
Formation, the technical issues of final film Ohmic resistance rises over time, and battery performance declines.
The utility model can reduce Fe (OH) by the chelating agent of the organic compound form of addition3The shape of precipitation
At.These organic compounds can form compound, wherein Fe3+It is transitioned into plating side from redox side.These compounds exist
It is more soluble in acidic environment, to stabilize iron ion.
In addition, the color and current potential of these complicated compounds are related to the pH value of solution.Therefore, the utility model passes through
The pH of optical sensor and/or electrochemical probe monitoring electrolyte, to realize the metering to the chemical addition agent of addition, with reality
Now with maintain electrolyte needed for pH, to prevent precipitate and preserve coulombic efficiency.
Here the description and application of the utility model are illustrative, are not wishing to the scope of the utility model being limited in
It states in embodiment.The deformation and change of embodiments disclosed herein are possible, for the ordinary skill people of those this fields
The replacement of embodiment and equivalent various parts are well known for member.It should be appreciated by the person skilled in the art that not taking off
In the case of spirit or essential characteristics from the utility model, the utility model can in other forms, structure, arrangement, ratio,
And it is realized with other components, material and component.It, can be to this in the case where not departing from the scope of the utility model and spirit
In disclosed embodiment carry out other deformations and change.
Claims (9)
1. a kind of iron-based redox flow battery system, which is characterized in that the battery system includes：Control system, plating
Electrolyte storage tank, redox electrolyte storage tank, first sensor, second sensor, the first external reservoir, the second outside storage
Tank, cathode additive pump, anode additive pump, cathode, anode, cathode plating iron layer, diaphragm, cathode reactor, anode reactor,
First probe, the second probe, first pump housing, second pump housing；
The control system be separately connected first sensor, second sensor, the first probe, the second probe, cathode additive pump,
Anode additive pump, first pump housing, second pump housing, the control system receive first sensor, second sensor, the first spy
The data of needle, the second probe induced, the action of control cathode additive pump, anode additive pump, first pump housing, second pump housing；
Electrolyte can be pumped out by first pump housing, second pump housing from reactor；
The first sensor, second sensor are used to determine the chemical property of electrolyte, including pH value, and are passed as optics
Sensor uses；First probe, the second probe are used to measure the chemical property of electrolyte；
The effect of the electroplating electrolytes storage tank, redox electrolyte storage tank is storage electrolyte；The effect of electrolyte be
It is chemically reacted in charging process, stores electricity, again discharge the charge in electrolyte in discharge process；
The effect of first external reservoir and the second external reservoir is that storage plating bath additive, redox are electric respectively
Matter additive is solved, when changing to the electrolyte ph in electroplating electrolytes storage tank, redox electrolyte storage tank, pump
Enter additive, to adjust pH value；
First external reservoir, the second external reservoir store cathode additive, anode additive respectively；First outside storage
Tank pumps connection cathode reactor by cathode additive, and the second external reservoir pumps jointed anode reactor by anode additive；
First external reservoir, the second external reservoir will can be fluidly coupled to cathode reactor, the anode reactor of battery system respectively；Electricity
Solution solution additive can be pumped into corresponding electroplating electrolytes storage tank, redox from the first external reservoir, the second external reservoir respectively
Electrolyte storage tank；
First pump housing is arranged by two piping connection cathode reactors, wherein a pipeline in the electroplating electrolytes storage tank,
First sensor is arranged in a pipeline wherein；
The redox electrolyte storage tank is pumped by two piping connection anode reactors, wherein a pipeline setting second
Body, wherein pipeline second sensor is set；
The cathode, cathode plating iron layer, cathode reactor, diaphragm, anode reactor, anode are set gradually；
The diaphragm is being isolated cloudy reactor, positive reactor and its respective electrolyte；The diaphragm is envelope barrier, is ion
Exchange membrane or microporous barrier are placed between redox electrolytes liquid and plating bath, with prevent electrolyte from intersecting and provide from
Subconductivity；
For the electroplating electrolytes storage tank to store plating bath, redox electrolyte storage tank is electric to store redox
Solve liquid；The plating bath and redox electrolytes liquid are all made of identical metal salt, and only its concentration is different；
The anode is oxidation-reduction electrode, will be fluidly coupled to redox electrolyte storage tank；The cathode is electroplated electrode,
It will be fluidly coupled to electroplating electrolytes storage tank.
2. a kind of iron-based redox flow battery system, which is characterized in that the battery system includes：Electroplated electrode, oxidation
Reducing electrode, electroplating electrolytes storage tank, redox electrolyte storage tank, first reactor, second reactor, the first outside storage
Tank, the second external reservoir, control system, monitoring device；
The electroplating electrolytes storage tank to store plating bath, to store oxidation go back by the redox electrolyte storage tank
Former electrolyte；
The oxidation-reduction electrode will be fluidly coupled to redox electrolyte storage tank, and the electroplated electrode will be fluidly coupled to electricity
Plate electrolyte storage tank；
The electroplating electrolytes storage tank connects first reactor by the first transfer pipeline, and redox electrolyte storage tank passes through the
Two transfer pipelines connect second reactor；The first reactor connects electroplated electrode, and the second reactor connection oxidation is also
Primary electrode；
The monitoring device is detecting in the electroplating electrolytes storage tank or/and in redox electrolyte storage tank or/and
The chemical property of one transfer pipeline or/and the second transfer pipeline Inner electrolysis matter；
The control system connects monitoring device, and the first external reservoir, the are controlled according to the data that the monitoring device monitors
The additive of two external reservoirs is pumped into toward electrolyte storage tank.
3. iron-based redox flow battery system according to claim 2, it is characterised in that：
The effect of the electroplating electrolytes storage tank, redox electrolyte storage tank is storage electrolyte；The effect of electrolyte be
It is chemically reacted in charging process, stores electricity, again discharge the charge in electrolyte in discharge process；
The effect of first external reservoir and the second external reservoir is that storage plating bath additive, redox are electric respectively
Matter additive is solved, is pumped when changing to the electrolyte ph in electroplating electrolytes storage tank, redox electrolyte storage tank
Enter additive, to adjust pH value.
4. iron-based redox flow battery system according to claim 2, it is characterised in that：
The battery system further includes cathode additive pump, anode additive pump, first pump housing, second pump housing；The control system
System is separately connected the first additive pump, Second addition pump, first pump housing, second pump housing；The first reactor is that cathode is anti-
It is anode reactor to answer device, second reactor；
First external reservoir, the second external reservoir store cathode additive, anode additive respectively；First outside storage
Tank pumps connection cathode reactor by cathode additive, and the second external reservoir pumps jointed anode reactor by anode additive；
First external reservoir, the second external reservoir will can be fluidly coupled to cathode reactor, the anode reactor of battery system respectively；
The electroplating electrolytes storage tank connects electroplated electrode by third transfer pipeline, and the third transfer pipeline is equipped with the first pump
Body；
The redox electrolyte storage tank connects oxidation-reduction electrode by the 4th transfer pipeline, and the 4th transfer pipeline is set
There is second pump housing.
5. iron-based redox flow battery system according to claim 2, it is characterised in that：
The monitoring device includes Fe potential probes, is connected with reference electrode by a clean iron wire.
6. iron-based redox flow battery system according to claim 2, it is characterised in that：
The monitoring device includes first sensor, second sensor, and first sensor is set to the first transfer pipeline, and second passes
Sensor is set to the second transfer pipeline；The first sensor, second sensor are used to determine the chemical property of electrolyte, including
PH value；Alternatively,
The monitoring device include the first probe, the second probe part be respectively arranged at electroplating electrolytes storage tank, redox
In electrolyte storage tank, the chemical property for measuring electrolyte.
7. iron-based redox flow battery system according to claim 2, it is characterised in that：
It is equipped with cathode between the electroplated electrode and first reactor and plates iron layer.
8. iron-based redox flow battery system according to claim 6, it is characterised in that：
Diaphragm is equipped between the first reactor and second reactor.
9. iron-based redox flow battery system according to claim 4, it is characterised in that：
The electroplated electrode is cathode, and the oxidation-reduction electrode is anode；It is set between the electroplated electrode and first reactor
There is cathode to plate iron layer；Diaphragm is equipped between the cathode reactor and anode reactor；The cathode, cathode plating iron layer, cathode
Reactor, diaphragm, anode reactor, anode are set gradually；
The diaphragm is being isolated cloudy reactor, positive reactor and its respective electrolyte；The diaphragm is envelope barrier, is ion
Exchange membrane or microporous barrier are placed between redox electrolytes liquid and plating bath, with prevent electrolyte from intersecting and provide from
Subconductivity；
For the electroplating electrolytes storage tank to store plating bath, redox electrolyte storage tank is electric to store redox
Solve liquid；The plating bath and redox electrolytes liquid are all made of identical metal salt, and only its concentration is different；
The anode is oxidation-reduction electrode, will be fluidly coupled to redox electrolyte storage tank；The cathode is electroplated electrode,
It will be fluidly coupled to electroplating electrolytes storage tank.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109428105A (en) * | 2017-08-30 | 2019-03-05 | 北京好风光储能技术有限公司 | A kind of tubular reactor for lithium flow battery |
| CN109879256A (en) * | 2019-03-26 | 2019-06-14 | 扬州大学 | A kind of Fe2+The electrochemical reactor that cathodic reduction is coupled with anodic oxidation |
-
2017
- 2017-12-22 CN CN201721814054.7U patent/CN207690927U/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109428105A (en) * | 2017-08-30 | 2019-03-05 | 北京好风光储能技术有限公司 | A kind of tubular reactor for lithium flow battery |
| CN109428105B (en) * | 2017-08-30 | 2020-12-08 | 北京好风光储能技术有限公司 | Tubular reactor for lithium flow battery |
| CN109879256A (en) * | 2019-03-26 | 2019-06-14 | 扬州大学 | A kind of Fe2+The electrochemical reactor that cathodic reduction is coupled with anodic oxidation |
| CN109879256B (en) * | 2019-03-26 | 2022-04-12 | 扬州大学 | Fe2+Electrochemical reactor with coupled cathode reduction and anode oxidation |
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